Fungicidal and acaricidal composition and method of use

ABSTRACT

Biocidal compositions containing as an active ingredient the compound of the formula   THE COMPOSITIONS ARE USEFUL FOR COMBATTING FUNGI, HELMINTHS AND ACARIDS.

United States Patent 1 1 0st et a].

11] 3,717,709 1 1 Feb. 20, 1973 [22] Filed:

[54] FUNGICIDAL AND ACARICIDAL COMPOSITION AND METHOD OF USE [75]Inventors: Walter Ost; Klaus Thomas; Dietrich Jerchel, all of Ingelheim,Rhine; Karl-Richard Appel, Biberach- Rissegg, all of Germany [63]Continuation-impart of Ser. No. 793,187, Jan. 22,

1969, Pat. No. 3,595,9l6.

Jan. 23. 1968 Austria ..a674/68 May 17. 1968 Austria ..a4795/68 [52] US.Cl ..424/250 [51] Int. Cl. ..A01n 5/00 [58] Field or Search ..424/250;260/268 R [56] References Cited UNITED STATES PATENTS PrimaryExaminer-Albert T. Meyers Assistant Examiner-Norman A. DrezinAttorneyHammond & Littell [57] ABSTRACT Biocidal compositions containingas an active ingredient the compound of the formula the compositions areuseful for combatting fungi, helminths and acarids.

2 Claims, No Drawings Dunbar ..424/250 AND METHOD OF USE 1,

This is a continuation-in-part of copending application Ser. No.793,187, filed Jan. 22, 1969, now U.S. Pat. No.3,595,916.

This invention relates to novel biocidal agricultural compositions andto a novel method of combatting fungi, helminths and acarids therewith.

More particularly, the present invention relates to novel biocidalcompositions containing as an active ingredien-t N,N '-bis-[(lformamido-2,2,2-trichloro ethyl]piperazine of the formula The compoundof the formula I may be prepared by methods involving well knownchemical principles,

among which the following has proved to be particularly convenient andefficient:

By reacting a compound of the formula or arylcarbonyloxy, withpiperazine, pursuant to the following reaction formula The reaction ispreferably carried out in the presence of an inert organic solvent, suchas tetrahydrofuran, dioxane, toluene, acetone or a chlorinatedhydrocarbon, at a temperature between about 20 and +l C., preferablybetween +20 and +40C.

When X in formula 11 is chlorine or bromine it is advantageous to add tothe reaction mixture an equivalent amount of a tertiary amine, such astriethylamine. In those instances it is assumed that a reactiveintermediate of the formula HCO-N= CH-CCl is formed, which then reactsfurther to undergo an addition reaction with the piperazine and forms acompound of the formula 1. I

The end product of the formula 1 thus obtained is a weak base; it is acolorless crystalline solid, sparsely soluble in water, but relativelyeasily soluble in dimethylsulfoxide, tetrahydrofuran, cyclohexanone,dimethylformamide, N-methyl-pyrrolidone and butyrolactone.

The starting compound of the formula 11 may be prepared pursuant toknown processes, such as by exchange of the hydroxyl group in a compoundof the formula HCONH-CHOH-CCI for a substituent X, as defined inconnection with formula 11 above.

The following examples further illustrate the present invention and willenable others skilled in the art to understand it more completely. Itshould be understood, however, that the invention is not limited solelyto the particular examples given below.

EXAMPLE 1 Preparation of N,N -bis-[( l-formamido-2,2,2-trichloro)-ethyl]-piperazine While stirring, a solution of 4.3 gm (0.05mol) of piperazine and 10.5 gm (0.104 mol) of triethylamine in 70 cc ofacetone was added dropwise to a solution of 21.1 gm (0.1 mol) of(l,2,2,2-tetrachloro-ethyl)-formamide in cc of acetone. Thereafter, thereaction mixture was allowed to stand at room temperature, and then theprecipitate consisting of the reaction product and triethylaminehydrochloride was separated by vacuum filtration, thoroughly washedfirst with water and then with cold methanol and finally dried at 40C.,yielding a colorless crystalline powder having a decomposition point ofabout 175C. (depending upon the rate of heating), which was identifiedto be N,N'-bislformamido-2,2,2,-trichloro)-ethyl]-piperazine.

A second fraction of this compound was obtained by evaporation of theacetonic mother liquor and washing of the residue with cold methanol.The total yield was 18.7 gm (86 percent of theory). The product wasrecrystallizable from dioxane.

Analysis:

Calculated: C 27.61%; H 3.24%; N 12.88% Found: C 27.90%; H 3.38%; N12.68%

EXAMPLE 2 EXAMPLE 3 5.3 gm (0.05 mol) of sodium carbonate were added toa solution of 21.1 gm (0.1 mol) of N-(l,2,2,2-tetrachloro-ethyl)-formamide in 50 cc of acetone, and then, whilestirring, a solution of 4.3 gm (0.05 mol) of piperazine in 50 cc ofacetone was added dropwise. Thereafter, the reaction mixture was stirredfor 30 minutes more, the acetone was distilled off in vacuo, and theresidue was washed first with water and then with cold methanol andfinally dried. The yield was 77 percent of theory ofN,N'-bis-[(l-formamido-2,2,2-

trichloro )-ethyl]-piperazine.

, methylmercapto-2,2,2-trichloro)-ethane,

EXAMPLE 4 A mixture consisting ,of 2.1 gm (0.025 mol) of piperazine, 5.1gm (0.05 mo1) of triethylamine, 6.8 gm (0.05 mol) of[(J-formamido2,2,2-trichloro)-ethoxy]- benzene and 50 cc of absolutetetrahydrofuran was allowed to stand for l4 hours at room temperature,and thereafter'was refluxed for 2 hours. Subsequently, the reactionsolution was filtered, the filtrate was evaporated invacuo, and. theviscous brown residue, which had an odor of phenol, was digested with 15cc of methanol. After several hours of standing, about percent of theoryof N,N-bis-[(1-formamido-2,2,2- trichloro)-ethyl]-piperazine hadcrystallized out.

The starting compound, l-formamido-2,2,2- trichloro)-ethoxyl]-benzene,m. p. 93- 94C., was obtained with ayield of 83 percent of theoryfrom N-[(1,2,2,2-tetrachloro)-ethyl]-formamide and phenol in the presence oftriethylamine.

and then with methanol. 96 percent of theory of N,N'-

bis-[( l-form amide-2,2,2-trichloro)-ethylJ-piperazine were obtained. Ii

The starting compound,,[ 1-formamido-l-(methylsulfonyl)-2,2,2-trichloro]-ethane, m. p, l32 '.l33C;, was prepared in the following manner:tetrachloro)-ethyl]-formamide was first reacted with methylmercaptan inthe presence of triethylamine, yielding 82 percentof theory of(l-formamido-lm. p. l22-123C., which was subsequently oxidized withhydrogen peroxide in acetic acid at 20 C. The yield was 66 percentof-theory. v

The compoundofthe formula 1 above has useful properties. Moreparticularly, it is a highly effective broadspectrum fungicide with verylow phyto-toxicity; thus it may be effectively used for prophylactic aswell as ourative treatment of plants against a wide variety ofphytopathogenic fungi. For instance, the compound exhibits fungitoxicactivities against genuine mildewfuh:

gi, such as Erysiphe graminis, E rysiphe polygoui, Erysiphecichoracetzrum, Sphaerotheca r pannosa, Podosphaera leucotricha, Oidium'fragariae, Qidium tuckeri, Sph'aeroteca mars uvae, and Sphaemthe'cafusca; against imperfect mildew fungi, such as Septoria api'i,CerCospora .beticala .and Cercospora rosae; against imperfect graymildewfuhgi, such as Botrytis cinerea; against -rust fungi, such asUromyces fabae, Puccinia' arenariae, Puccinia i pelargom'i, *Phragmidiummucronatum and Puccinia 'recondita; against Marssonina rqsaqagainstcauses of wilting diseases, such as Verticillium alboatrum; againstcauses of plant scabs, such as Venturia inaequalis;.against mold fungi,such as Aspergillus niger; and various other harmful fungi, suchasFuraria spec., Ophiobuli, Claviceps purpurea and Gloetinia temulenta.

Particularly noteworthy is the good systemic effect of the compound.

The compound of the formula [is also useful as an anthelmintic andenhances the germination of seeds, such as pea and cotton seeds.

The compound of the formula 1 is, in addition, a highly effectiveacaricide and may thus also be effectively used for combattinginfestation by harmful crustacean pests, such as aphids and weevils(e.g. Calandra, gra nar ia), cimeces (e.g. Cimex lectularius), roaches(e.g.1Phyllodroma germanica) and spider mites (e.g.. Tetranychusurticae).

Of particular importance is the surprisingly excellent effectivenessagainst spider mites; the compound evidently kills these pests in thelarva stage and thereby effectively decimates the population.

The successful eradication of spider mites is of special importance inagriculture, particularly in fruit orchards and the like, becausesignificant spider mite infestation may cause substantial harvestreductions. For this reason a number of pesticidal compositions havebeen developed which effectively kill spider mites. Such acaricidalcompositions contain as active ingredients, for example,2-sec.butyl-4,6-dinitrophenyl-(2-methylcrotonat e) and2,4,5,4'-tetrachlorodiphenylsulfone. A number of organic phosphoric acidestersand carbamic acid esters also exhibit significant activity againstspider mites. Howeven after prolonged use of the known acaricides, ithas frequently been observed that spider mites develop a resistanceagainst them. The compound of the formula 1 and the compositions of theinvention containing it are particularly effective against theseresistant spider mites. The development of a resistance against thecompositions of the instant invention has so far not been observed and,by virtue of their mechanism of action, is also not expected.

Agricultural and ornamental plants often become simultaneously infestedwith spider mites as well as phytogenic fungi, which heavily damages theaffected plants and may lead to substantial losses. The causativemicroorganisms of the fungus infections are either completely unaffectedby the known acaricidal agents or their growth is inhibited only to aminor degree. Consequently, it has heretofore been customary and,indeed, necessary to apply fungicides in addition to acaricides, oftenusing several different active ingredie nts simultaneously orsuccessively, in order to combat different, simultaneously occurringfungus diseases.

ingredient into customary fungicidal compositions, i.e. I

compositions consisting essentially of a liquid or comminuted solidinert carrier, and an effective fungicidal and acaricidal amount of theactive ingredient, such as solutions, emulsion concentrates, 1suspendable or wettable powders, dusting powders, granulates and sprays.The active ingredient content of these composi- By virtue of the factthat the compound of the formutions is about 0.05 to 85 percent byweight, preferably 0.5 to 50 percent by weight.

For instance, an emulsion concentrate contains about 0.5 to 20 percentby weight, preferably 5 to percent by weight, of the compound of theformula 1. Suitable solvents for the preparation of emulsionconcentrates comprising the compound of the formula I as an activeingredient are, for example, mixtures of dimethylformamide orN-methylpyrrolidone with alcohols or glycols. Suitable emulsifiers andwetting agents which may be used for the preparation of such emulsionconcentrates are non-ionic compounds, such as nonylphenol polyglycolether, or mixtures of nonionic and ionic, preferably anionic, compoundsas well as ampholytes. The emulsifier content of the emulsionconcentrate is about 0.5 to 45 percent by weight, preferably 5 to 25percent by weight.

The active ingredient content of a wettable powder is about 0.5 to 80percent by weight, preferably to 60 percent by weight. Suitableemulsifiers and wetting agents which may be used for the preparation ofwettable powders are non-ionic or ionic compounds of the type describedin the preceding paragraph; the total amount of emulsifier and wettingagent in such wettable powders is about 0.5 to percent by weight,preferably 2 to 25 percent by weight. Suitable powdery inert carriersare, for example, bentonite, kaolin and colloidal silicic acid.

The fungicidal and acaricidal compositions of the present invention are,if necessary, diluted with water to an active ingredient concentrationof 0.5 to 0.0001 percent prior to their use for combatting fungi andacarids. Dusting powders may have a higher active ingredientconcentration. The upper limit for the application concentration ispredicated upon the relatively low phytotoxicity.

The following examples illustrate a few fungicidal and acaricidalcompositions comprising a compound of the instant invention as an activeingredient and represent the best mode contemplated of putting theinvention to practical use. The percentages are percent by weight.

EXAMPLE 6 Dusting Powder N,N '-Bis-[( l-formamido-2,2,2-

trichloro )-ethyl l-piperazine 1% Talcum 98% Methylcellulose 1% Thecomponents are admixed with each other, and the mixture is milled untilhomogeneous.

EXAM PLE 7 Wettable Powder (a) N,N'-Bis-[( l-formamido 2,2,2

trichloro)-ethyl]-piperazine 25% Kaolin 55% Colloidal silicic acid 10%Lignin sulfonate (dispersing agent) 9% Sodium tetrapropylene benzenesulfonate (wetting agent) 1% or (b) N,N'-Bis-[( lformamido-2,2.2

trichloro)-ethyl]-piperazine 80% Colloidal Silicic acid 5% Sodium ligninsulfonate 5 Sodium diisobutylnaphthalene sulfonate 1% Urea 9% Thecomponents are admixed, the mixture is milled until homogeneous, andprior to use the powder is suspended in an amount of water such that theactive ingredient concentration in the aqueous suspension is from 0.0001to 0.5 percent by weight.

EXAMPLE 8 Emulsion Concentrate N,N,'-Bis-[( l -formamido-2,2,2-

trichloro)-ethyl]-piperazine 10% Sodium tetrapropylene benzene Sulfonate(anionic emulsifier) 5% Nonylphenol polyglycol ether 20% (non-ionicemulsifier) Propyleneglycol 32.5% N-Methylpyrrolidone 32.5%

The components are uniformly admixed with each other, and prior to usethe resulting concentrate is diluted with water to the desired activeingredient content between 0.0001 and 0.5 percent by weight.

EXAMPLE 9 Aerosol Spray (a) N,N'Bis-[(l-fonnamido-2,2,2-

trichloro)-ethyl]-piperazine 0.05% Sesame oil 0.10% N-Methylpyrrolidon 10.00% Propellant gas 89.85% or (b) N,N'-Bis-[(l-formamido-2,2,2-

trichloro )-ethyl]-piperazine 0.1% Ethanolamine salt ofdodecylbenzenesulfonic acid 0.5% N-Methylpyrrolidone 10.0% Propellantgas 88.5%

The components are admixed in customary fashion, and the mixture ischarged into aerosol containers provided with a spray valve.

EXAMPLE l0 Water-soluble Concentrate N,N'-Bis-[( l-fonnamido-2,2,2-

trichloro)-ethyl]-piperazine 20% Ethanolarnine salt of dodecylbenzenesulfonic acid 20% Dimethylformamide 64% The ingredients are intimatelyadmixed with each other, and prior to use the resulting concentrate isdissolved in an amount of water such that the active ingredientconcentration in the aqueous solution is between 0.0001 and 0.5 percentby weight.

EXAMPLE ll Ultra-low-volume Concentrate N,N'-Bis[( lformamido-2,2,2-

trichloro)-ethyll-piperazine 18% Triethyleneglycol 30%N-Methylpyrrolidone 44% Condensation product of 1 mol of nonylphenolwith 5 mols of ethyleneoxide 8% acarids, which comprises contacting saidfungi and acarids with an effective fungicidal and acaricidal amount ofN,N'-bis-[(l-formamido-2,2,2-trichloro)- ethyl]-piperazine.

Em- I. I" I.

First Page, insert --[30] Foreign Application Priority Data 223 IUNITED-STATES PA'rmr Uri-1cm CERTIFICATE OF CORRECTION "D t d Feb.

stem: No.

WALTER 0ST, KLAUS THOMAS, DIETRICH JERCHEL and KARL-RTEHARU APPEL v eabove-identified patent it is certified that error appears in th that.said Letters Patent are hereby corrected as shown below:

Jan. 23, 1968 Austria 1968 Austria A l795/68 May 17, I July 3, 1970Austria A6026/7O First Page, [73] -.4 correct "Brehreng er" to read --Boehringer--.

Col. 3, line 16 correct "ethoxylJ" to read ethoxy]-.

" before line 20, insert -EXAMPLE 5.

Signed and sealed this 20th day of November 1973.

(SEAL) Attest:

EDWARD M.FLET0HER ,JR. RENE D. TEG'TMEYER Attesting Officer ActingCommissioner of Patents

1. A fungicidal and acaricidal composition consisting essentially ofinert carrier and an effective fungicidal and acaricidal amount ofN,N''-bis-((1-formamido-2,2,2-trichloro)-ethyl)-piperazine.